Ethers on esters of 1-triazole-2-substituted ethanols

ABSTRACT

A compound of general formula (1) ##STR1## wherein R 1  is C 1-6  alkyl, cyclobutyl, cyclopropyl, cyclopentyl cyclohexyl or phenyl, and R 2  is phenyl or benzyl; the phenyl of R 1  and the phenyl or phenyl moiety of the benzyl of R 2  being optionally substituted with halogen, C 1-6  alkyl, C 1-5  alkoxy, C 1-10  alkoxyalkyl, halo-C 1-4  alkyl, halo-C 1-4  alkoxy, halo- 1-5  alkoxy, halo-C 1-5  alkyl, nitro, phenyl, phenoxy, benzyl, optionally halo-substituted benzyloxy, C 1-2  alkylenedioxy, acetylamino, halo-C 1-2  alkylenedioxy, amino, mono- or di-C 1-4  alkylamino, hydroxy, cyano, morpholino or carboxy or an alkyl ester thereof, and/or the alkyl moiety of the benzyl is optionally substituted with one C 1-4  alkyl; and acid addition salts, ethers, esters and metal complexes thereof. The compounds are useful as fungicides and as plant growth regulating agents.

This application is a continuation of Ser. No. 907,180, filed Sept. 16,1986, now abandoned, which is itself a continuation of Ser. No. 593,271,filed Mar. 26, 1984, now abandoned, which is itself a continuation ofSer. No. 293, 338, filed Aug. 17, 1981, now abandoned, which is acontinuation-in-part of Ser. No. 183,140, filed Sept. 3, 1980, now U.S.Pat. No. 4,551,469, which itself is a continuation-in-part of Ser. No.124,253, filed Feb. 25, 1980, now U.S. Pat. No. 4,654,332.

This invention relates to triazole compounds useful as fungicides andplant growth regulating agents, to a process for preparing them, tofungicidal and plant growth regulating compositions containing them, andto a method of combating fungi, especially fungal infections in plants,and to a method for regulating the growth of plants using them.

The invention provides a triazole compound having the general formula(I): ##STR2## wherein R¹ is C₁₋₆ alkyl, cyclobutyl, cyclopropyl,cyclopentyl, cyclohexyl or phenyl, and R² is phenyl or benzyl; thephenyl of R¹ and the phenyl or phenyl moiety of the benzyl of R² beingoptionally substituted with halogen, C₁₋₆ alkyl, C₁₋₅ alkoxy, C₁₋₁₀alkoxyalkyl, halo- C₁₋₄ alkyl, halo- C₁₋₄ alkoxy, halo- C₁₋₅ alkoxyhalo- C₁₋₅ alkyl, nitro, phenyl, phenoxy, benzyl, optionallyhalo-substituted benzyloxy, C₁₋₂ alkylenedioxy, acetylamino, halo- C₁₋₂alkylenedioxy, amino, mono- or di- C₁₋₄ alkylamino, hydroxy, cyano,morpholino or carboxy or an alkyl ester thereof, and/or the alkyl moietyof the benzyl is optionally substituted with one C₁₋₄ alkyl; and acidaddition salts/ethers; esters and metal complexes thereof.

The compounds of the invention can contain chiral centres. Suchcompounds are generally obtained in the form of racemic mixtures.However, these and other mixtures can be separated into individualisomers by methods known in the art.

In a further aspect the invention provides a method as defined abovewherein R¹ is C₁₋₄ alkyl and R² is optionally substituted benzyl.

In another aspect the invention provides a method as described abovewherein R¹ is optionally substituted phenyl and R² is optionallysubstituted benzyl.

In a yet further aspect the invention provides a method as defined abovewherein R¹ and R², which may be the same or different, is optionallysubstituted phenyl.

In a still further aspect the invention provides a method as definedabove wherein R¹ is C₁₋₄ aklyl and R² is optionally substituted phenyl.

When R¹ is alkyl it can be a straight or branched chain group having 1to 6, e.g. 1 to 4 carbon atoms; examples are methyl, ethyl, propyl (n-or iso-propyl), butyl (n-, sec-, iso- or t-butyl), pentyl (e.g.n-pentyl) and hexyl (e.g. n-hexyl). It is preferably butyl, especiallyt-butyl.

Examples of suitable substituents for the phenyl and for the phenylmoiety of the benzyl are halogen (e.g. fluorine, chlorine or bromine),C₁₋₅ alkyl [e.g. methyl, ethyl, propyl (n- or iso-propyl) and butyl (n-,sec-, iso-or t-butyl], C₁₋₄ alkoxy (e.g. methoxy and ethoxy), halo- C₁₋₄alkyl (e.g. trifluoromethyl or 1, 1, 2, 2-tetrafluoroethyl), halo- C₁₋₄alkoxy (e.g. trifluoromethoxy or 1, 1, 2, 2-tetrafluoroethoxy), nitro,phenyl, phenoxy, benzyl, benzyloxy (optionally ring substituted withhalogen), alkylenedioxy, haloalkylenedioxy (e.g.difluoromethylenedioxy), amino, mono- or di- C₁₋₄ alkylamino (e.g.dimethylamino), hydroxy, morpholino and carboxy (and alkyl estersthereof). The alkyl moiety of the benzyl can be substituted with forexample one alkyl (e.g. methyl or ethyl). Suitably the phenyl and benzylare unsubstituted or substituted with 1, 2 or 3 ring substitutents asdefined above. Preferably the benzyl and phenyl have a single ringsubstituent in the 2- or 4- position. Examples of these groups arephenyl, benzyl, -methylbenzyl, 2-, 3- or 4-chlorophenyl, 2,4- or2,6-dichlorophenyl, 2-, 3- or 4-fluorophenyl, 2,4- or2,6-difluorophenyl, 2-, 3- or 4-bromophenyl, 2-chloro-4-fluorophenyl,2-fluoro-4-chlorophenyl, 2-chloro-6-fluorophenyl, 2-, 3- or4-methoxyphenyl, 2, 4-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3-or 4-nitrophenyl, 2-chloro-4-nitrophenyl, 2-chloro-5-nitrophenyl, 2-, 3-or 4-methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-t-butylphenyl, 2-, 3-or 4-trifluoromethylphenyl, 2-, 3- or 4-trifluoromethoxyphenyl, 2-, 3-or 4-(1,1,2,2-tetrafluoroethyl)phenyl, 2,3-(difluoromethylenedioxyphenyl), 2-fluoro-4-methoxyphenyl, 2-methoxy- 4-fluorophenyl,2-methoxy-4-chlorophenyl, 2-methoxy-4-fluorophenyl, 2-, 3- or4-phenoxyphenyl, 2-, 3-or 4-phenylphenyl (2-, 3- or 4-bisphenylyl), 2-,3- or 4-benzylphenyl, 2-, 3- or 4-benzyloxyphenyl, 2-, 3- or4-(4-chloro-or 4-fluorobenzyloxy)phenyl, 2-, 3- or 4-aminophenyl, 2-, 3-or 4-(N,N-dimethylamino)phenyl, 2-, 3- or 4-hydroxyphenyl, 2-, 3- or4-carboxyphenyl, 2-, 3- or 4-(methoxycarbonyl)phenyl, 2-, 3- or4-morpholinophenyl and the corresponding ring substituted benzyl andα-methyl benzyl groups.

In a further aspect, therefore the invention provides compounds asdefined above wherein R¹ and R² are both halophenyl and preferably onewherein R¹ and R², which may be the same or different, are eachchlorophenyl or fluorophenyl.

Furthermore in another aspect the invention provides compounds asdefined above wherein at least one phenyl ring also bears one or morealkoxy groups, and, for example R¹ may be 2-chloro-4-methoxyphenyl whenR² is 2-chloro-, 2-fluoro, 4-chloro- or 4-fluoro-phenyl.

Preferred compounds according to the invention are:1-(1,2,4-triazol-1-yl)-2-(4-fluorophenyl)2-(4-chlorophenyl)ethan-2-ol;1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)ethan-2-ol;1-(1,2,4-triazol-1-yl)-2-(4-fluorophenyl)-2-(2,4-dichlorophenyl)ethan-2-ol;1-(1,2,4-triazol-1-yl)-2,2-di(4-fluorophenyl)ethan-2-ol;1-(1,2,4-triazol-1-yl)-2-(4-chlorophenyl)-2-(2-chlorophenyl)ethan-2-ol;1-(1,2,4-triazol-1-yl)-2(4-fluorophenyl)-2-(2-chlorophenyl)ethan-1-ol;2,2-dimethyl-3-(2-methoxybenzyl)-4-(1,2,4-triazol-1-yl)-butan-3-ol;1-(1,2,4-triazol-1-yl)-2-(2-chloro-4-methoxyphenyl)-2-(4-fluorophenyl)ethan-2-ol;1-(1,2,4-triazol-1-yl)-2-(4-chlorophenyl)-3,3-dimethyl-butan-2-ol;1-(1,2,4-triazol-1-yl)-bis-2-(4-fluorophenyl)-2-methoxy-ethane;1-(1,2,4-triazol-1-yl)-2-(4-fluorophenyl2-(2-fluoro-4-methyl-phenyl)ethan-2-ol;1-(1,2,4-triazol-1-yl)2-(4-fluorophenyl)-2-(2-chloro-4-methyl-phenyl)ethan-2-ol;

The invention includes ethers and esters of compounds defined above.Preferred ethers are C₁₋₆ alkyl ethers, C₃₋₄ alkenyl ethers,optionally-substituted benzyl ethers, for example, methyl, ethyl,propyl, butyl, amyl, hexyl, allyl, benzyl and chlorobenzyl ethers. Thus,in the case of the benzyl ethers, the benzyl may be unsubstituted orsubstituted with chlorine. These may be straight or branched chainradicals or groups. Particularly preferred are the methyl ethers,especially the methyl ethers of the preferred, and specific compounds,set out herein. As regards esters these may be alkanyoyl, alkenoyl,alkynoyl or aroyl esters, for example, acetyl, acryloyl, crotonoyl,ethanoyl, propionoyl, butyryl, benzoyl, halo- or nitro- substitutedbenzoyl esters and, again, where appropriate these may be straight orbranched chain radicals or groups.

The salts can be salts with inorganic or organic acids e.g.hydrochloric, nitric, sulphuric, acetic, p-toluenesulphonic or oxalicacid.

Suitably the metal complex is one including, as the metal, copper, zinc,manganese or iron. It preferably has the general formula: ##STR3## whereY, R¹ and R² are as defined above, M is a metal, A is an anion (e.g. achloride, bromide, iodide, nitrate, sulphate or phosphate anion), n is 2or 4, y is 0 or an integer of 1 to 12, and m is an integer consistentwith valency.

Examples of the compounds of the invention are shown in Table I.

                                      TABLE I                                     __________________________________________________________________________    COMPOUND NO                                                                             R.sup.1          R.sup.2        MELTING POINT                       __________________________________________________________________________                                              (°C.)                        1         C.sub.6 H.sub.5  C.sub.6 H.sub.5 CH.sub.2                                                                     124-125                             2         C.sub.6 H.sub.5  p-ClC.sub.6 H.sub.4 CH.sub.2                                                                 144-145                             3         C.sub.6 H.sub.5  p-FC.sub.6 H.sub.4 CH.sub.2                                                                  116-118                             4         p-ClC.sub.6 H.sub.4                                                                            p-ClC.sub.6 H.sub.4 CH.sub.2                                                                 80-83                               5         p-Cl-C.sub.6 H.sub.4                                                                           C.sub.6 H.sub.5 CH.sub.2                                                                     109-111                             6         p-FC.sub.6 H.sub.4                                                                             C.sub.6 H.sub.5 CH.sub.2                                                                     141-142                             7*        C.sub.6 H.sub.5  2,4-diClC.sub.6 H.sub.3 CH.sub.2                                                             104-106                             8         p-FC.sub.6 H.sub.4                                                                             p-FC.sub.6 H.sub.4 CH.sub.2                                                                  154-156                             9         p-FC.sub.6 H.sub.4                                                                             p-ClC.sub.6 H.sub.4 CH.sub.2                                                                 168-170                             10        t-Bu             C.sub.6 H.sub.5 CH.sub.2                                                                     110-111                             11        t-Bu             p-ClC.sub.6 H.sub.4 CH.sub.2                                                                 86-87                               12        t-Bu             p-FC.sub.6 H.sub.4 CH.sub.2                                                                  146-148                             13        C.sub.6 H.sub.5  o-FC.sub.6 H.sub.4 CH.sub.2                                                                  133-134                             14        p-ClC.sub.6 H.sub.4                                                                            o-FC.sub.6 H.sub.4 CH.sub.2                                                                  95-96                               15        C.sub.6 H.sub.5  o-ClC.sub.6 H.sub.4 CH.sub.2                                                                 69-71                               16        p-MeOC.sub.6 H.sub.4                                                                           C.sub.6 H.sub.5 CH.sub.2                                                                     100-103                             17        C.sub.6 H.sub.5  C.sub.6 H.sub.5                                                                              128-129                             18.sup.+  p-FC.sub.6 H.sub.4                                                                             p-FC.sub.6 H.sub.4 CH.sub.2                                                                  161-163                             19        C.sub.6 H.sub.5  2,4-diClC.sub.6 H.sub.3 CH.sub.2                                                             104-106                              *Includes 1 mole of C.sub.2 H.sub.5 OH                                        .sup.+ This compound is a different crystalline form of compound no. 8   

    20        t-Bu             o-ClC.sub.6 H.sub.4 CH.sub.2                                                                 74-75                               21        t-Bu             O-FC.sub.6 H.sub.4 CH.sub.2                                                                  96-98                               22        t-Bu             m-ClC.sub.6 H.sub.4 CH.sub.2                                                                 88-89                               23        t-Bu             m-CF.sub.3C.sub.6 H.sub.4 CH.sub.2                                                           106-107                             24        C.sub.6 H.sub.5  p-t-Bu C.sub.6 H.sub.4 CH.sub.2                                                              80-83                               25        p-ClC.sub.6 H.sub.4                                                                            C.sub.6 H.sub.5                                                                              83-85                               26        p-ClC.sub.6 H.sub.4                                                                            p-ClC.sub.6 H.sub.4                                                                          147-148                             27        p-ClC.sub.6 H.sub.4                                                                            p-FC.sub.6 H.sub.4                                                                           154-155                             28        2,4-diClC.sub.6 H.sub.3                                                                        C.sub.6 H.sub.5                                                                              191-194                             29        p-FC.sub.6 H.sub.4                                                                             p-FC.sub.6 H.sub.4                                                                           170-171                             30        p-FC.sub.6 H.sub.4                                                                             C.sub.6 H.sub.5                                                                              139-140                             31        i-Bu             C.sub.6 H.sub.5                                                                              94-95                               32        n-Bu             p-ClC.sub.6 H.sub.5                                                                          95-97                               33        t-Bu             2-Cl6-FC.sub.6 H.sub.3 CH.sub.2                    34        t-Bu             2-Cl4-FC.sub.6 H.sub.3 CH.sub.2                                                              95                                  35        t-Bu             2-F4-ClC.sub.6 H.sub.3 CH.sub.2                                                              104-106                             36        t-Bu             2,4-diClC.sub.6 H.sub.3 CH.sub.2                   37        t-Bu             2,6-diClC.sub.6 H.sub.3 CH.sub.2                   38        t-Bu             2,6-diFC.sub.6 H.sub.3 CH.sub.2                    39        p-OCF.sub.2 HC.sub.6 H.sub.4                                                                   C.sub.6 H.sub.5                                                                              glass                               40        C.sub.6 H.sub.5  p-t-BuC.sub.6 H.sub.4                                                                        131-135°                     41        C.sub.6 H.sub.5  o-ClC.sub.6 H.sub.4                                                                          142-143°                     42        C.sub.6 H.sub.5  o-FC.sub.6 H.sub.4                                                                           126-128°                     43        p-ClC.sub.6 H.sub.4                                                                            o-ClC.sub.6 H.sub.4                                                                          137-138°                     44        p-ClC.sub.6 H.sub.4                                                                            o-FC.sub.6 H.sub.4                                                                           144-145°                     45        p-FC.sub.6 H.sub.4                                                                             o-ClC.sub.6 H.sub.4                                                                          115-116°                     46        p-FC.sub.6 H.sub.4                                                                             o-FC.sub.6 H.sub.4                                                                           120-123°                     47        C.sub.6 H.sub.5  o-C.sub.6 H.sub.5 OC.sub.6 H.sub.4                 48        p-ClC.sub.6 H.sub.4                                                                            o-C.sub.6 H.sub.5 OC.sub.6 H.sub.4                 49        C.sub.6 H.sub.5  o-MeC.sub.6 H.sub.4                                                                          161-162°                     50        p-ClC.sub.6 H.sub.4                                                                            o-MeC.sub.6 H.sub.4                                                                          157-158°                     51        2,4-diClC.sub.6 H.sub.3                                                                        p-FC.sub.6 H.sub.4                                                                           137-138°                     52        o-ClC.sub.6 H.sub.4                                                                            p-MeOC.sub.6 H.sub.4                                                                         184-185°                     53        2,4-diClC.sub.6 H.sub.3                                                                        p-ClC.sub.6 H.sub.4                                                                          174-175°                     54        2,4-diClC.sub.6 H.sub.3                                                                        o-ClC.sub.6 H.sub.4                                                                          149-151°                     55        2,4-diClC.sub.6 H.sub.3                                                                        o-FC.sub.6 H.sub.4                                                                           146-147°                     56        p-C.sub.6 H.sub.5 CH.sub.2 OC.sub.6 H.sub.4                                                    C.sub.6 H.sub.5                                                                              134-136°                     57        p-(p-ClC.sub.6 H.sub.4 CH.sub.2 O)                                                             C.sub.6 H.sub.5                                                                              98-100°                                C.sub.6 H.sub.4                                                     58        m-ClC.sub.6 H.sub.4                                                                            p-ClC.sub.6 H.sub.4                                                                          139-142°                     59        p-(p-FC.sub.6 H.sub.4 CH.sub.2 O)                                                              C.sub.6 H.sub.5                                                                              105-107°                               C.sub.6 H.sub.4                                                     60        m-ClC.sub.6 H.sub.4                                                                            p-FC.sub.6 H.sub.4                                                                           190-193°                     61        m-ClC.sub.6 H.sub.4                                                                            p-MeOC.sub.6 H.sub.4                                                                         58-60°                       62        2,4-diClC.sub.6 H.sub.3                                                                        m-ClC.sub.6 H.sub.4                                                                          139-142°                     63        o-MeC.sub.6 H.sub.4                                                                            p-FC.sub.6 H.sub.4                                                                           200-201°                     64        p-FC.sub.6 H.sub.4                                                                             p-CO.sub.2 CH.sub.3C.sub.6 H.sub.4                                                           164-166 (HCl Salt)                  65        p-OC.sub.2 H.sub.5C.sub.6 H.sub.4                                                              p-ClC.sub.6 H.sub.4                                                                          126-127°                     66        p-OCF.sub.2 HC.sub.6 H.sub.4                                                                   p-ClC.sub.6 H.sub.4                                                                          glass                               67        p-OCF.sub.2 HC.sub.6 H.sub.4                                                                   o-ClC.sub.6 H.sub.4                                                                          glass                               68        o-BrC.sub.6 H.sub.4                                                                            C.sub.6 H.sub.5                                    69        o-BrC.sub.6 H.sub.4                                                                            p-ClC.sub.6 H.sub.4                                                                          151-152°                     70        o-BrC.sub.6 H.sub.4                                                                            p-FC.sub.6 H.sub.4                                                                           109-111°                     71        p-NO.sub.2C.sub.6 H.sub.4                                                                      C.sub.6 H.sub.5                                                                              164-166°                     72        2-Cl5-NO.sub.2C.sub.6 H.sub.3                                                                  C.sub.6 H.sub.5                                                                              206-208°                     73        2-Cl4-NO.sub.2C.sub.6 H.sub.3                                                                  p-ClC.sub.6 H.sub.4                                74        o-NH.sub.2C.sub.6 H.sub.4                                                                      C.sub.6 H.sub.5                                    75        p-MeC.sub.6 H.sub.4                                                                            C.sub.6 H.sub.5                                                                              125-127°                     76        o-CO.sub.2 HC.sub.6 H.sub.4                                                                    p-FC.sub.6 H.sub. 4                                77        o-CO.sub.2 MeC.sub.6 H.sub.4                                                                   p-FC.sub.6 H.sub.4                                 78        o-CO.sub.2 HC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                    79        o-CO.sub.2 MeC.sub.6 H.sub.4                                                                   C.sub.6 H.sub.5                                    80        o-OHC.sub.6 H.sub.4                                                                            C.sub.6 H.sub.5                                    81        o-MeOC.sub.6 H.sub.4                                                                           C.sub.6 H.sub.5                                                                              113-116°                     82        o-MeOC.sub.6 H.sub.4                                                                           p-ClC.sub.6 H.sub.4                                                                          129-131°                     83        o-MeOC.sub.6 H.sub.4                                                                           p-FC.sub.6 H.sub.4                                                                           133-135°                     84        p-OHC.sub.6 H.sub.4                                                                            C.sub.6 H.sub.5                                    85        p-BrC.sub.6 H.sub.4                                                                            C.sub.6 H.sub.5                                                                              104-105°                     86        p-BrC.sub.6 H.sub.4                                                                            p-BrC.sub.6 H.sub.4                                                                          159-160°                     87        p-BrC.sub.6 H.sub.4                                                                            p-ClC.sub.6 H.sub.4                                                                          138-139°                     88        p-(CH.sub.3).sub.2 NC.sub.6 H.sub.4                                                            C.sub.6 H.sub.5                                    89        o-MeC.sub.6 H.sub.4                                                                            p-MeC.sub.6 H.sub.4                                                                          117-120°                     90        o-ClC.sub.6 H.sub. 4                                                                           p-MeC.sub.6 H.sub.4                                                                          169-170°                     91        o-FC.sub.6 H.sub.4                                                                             p-MeC.sub.6 H.sub.4                                                                          156-158°                     92        o-BrC.sub.6 H.sub.4                                                                            p-MeC.sub.6 H.sub.4                                93        o-NH.sub.2C.sub.6 H.sub.4                                                                      p-ClC.sub.6 H.sub.4                                94        o-CO.sub.2 HC.sub.6 H.sub.4                                                                    p-MeC.sub.6 H.sub.4                                95        o-CO.sub.2 MeC.sub.6 H.sub.4                                                                   p-MeC.sub.6 H.sub.4                                96        p-MOC.sub.6 H.sub.4                                                                            C.sub.6 H.sub.5                                    97        p-FC.sub.6 H.sub.4                                                                             p-NO.sub.2C.sub.6 H.sub.4                                                                    145-148°                     98        o-CO.sub.2 HC.sub.6 H.sub.4                                                                    p-BrC.sub.6 H.sub.4                                99        o-CO.sub.2 MeC.sub.6 H.sub.4                                                                   p-BrC.sub.6 H.sub.4                                100       o-CO.sub.2 HC.sub.6 H.sub.4                                                                    p-ClC.sub.6 H.sub.4                                101       o-CO.sub.2 MeC.sub.6 H.sub.4                                                                   p-ClC.sub.6 H.sub.4                                102       p-MeC.sub.6 H.sub.4                                                                            p-MeC.sub.6 H.sub.4                                                                          153-154°                     103       2,4-diMeC.sub.6 H.sub.3                                                                        C.sub.6 H.sub.5                                                                              148-9°                       104       m-NO.sub.2C.sub.6 H.sub.4                                                                      C.sub.6 H.sub.5                                                                              212-215° (HCl salt)          105       o-ClC.sub.6 H.sub.4                                                                            o-ClC.sub.6 H.sub.4                                                                          164-166°                     106       o-CF.sub.3C.sub.6 H.sub.4                                                                      C.sub.6 H.sub.5                                    107.sup.+ m-CF.sub.3C.sub.6 H.sub.4                                                                      C.sub.6 H.sub.5                                                                              115-117°                     108       p-CF.sub.3C.sub.6 H.sub.4                                                                      C.sub.6 H.sub.5                                                                              207-210° (HCl salt)          109       m-CF.sub.3C.sub.6 H.sub.4                                                                      p-ClC.sub.6 H.sub.4                                                                          104-106°                     110       p-OCF.sub.3C.sub.6 H.sub.4                                                                     C.sub.6 H.sub.5                                                                              glass                               111       p-OCF.sub.3C.sub.6 H.sub.4                                                                     p-ClC.sub.6 H.sub.4                                                                          107-108°                     112       p-OCF.sub.3C.sub.6 H.sub.4                                                                     o-ClC.sub.6 H.sub.4                                                                          99-100°                      113       p-OCF.sub.3C.sub.6 H.sub.4                                                                     p-OCF.sub.3C.sub.6 H.sub.4                         114       m-OCF.sub.3C.sub.6 H.sub.4                                                                     C.sub.6 H.sub.5                                    115       m-OCF.sub.3C.sub.6 H.sub.4                                                                     p-ClC.sub.6 H.sub.4                                116       m-OCF.sub.3C.sub.6 H.sub. 4                                                                    p-BrC.sub.6 H.sub.4                                117       o-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4                                                           C.sub.6 H.sub.5                                                                              188-189°                     118       o-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4                                                           p-ClC.sub.6 H.sub.4                                                                          94-95°                       119       m-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4                                                           C.sub.6 H.sub.5                                    120       m-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4                                                           p-ClC.sub.6 H.sub.4                                121       p-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4                                                           C.sub.6 H.sub.5                                                                              glass                               122*      p-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4                                                           p-ClC.sub.6 H.sub.4                                                                          glass                               123       p-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4                                                           p-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4                                                         glass                               124       3,4-ZC.sub.6 H.sub.4                                                                           C.sub.6 H.sub.5                                     .sup.+ melting point of HCl salt of this compound is                          *melting point of the 1:1 complex of this compound with isopropyl alcohol     is 74.5-77.5°.                                                        125       3,4-ZC.sub.6 H.sub.4                                                                           p-ClC.sub.6 H.sub.4                                                                          Glass                               126       3,4-ZC.sub.6 H.sub.4                                                                           o-ClC.sub. 6 H.sub.4                               127       3,4-ZC.sub.6 H.sub.4                                                                           p-FC.sub.6 H.sub.4                                 128       t-Bu             o-BrC.sub.6 H.sub.4 CH.sub.2                                                                 111-115°                     129       t-Bu             2,4-diFC.sub.6 H.sub.3 CH.sub.2                                                              140°                         130       t-Bu             o-MeOC.sub.6 H.sub.4 CH.sub.2                                                                113-116°                     131       Me               C.sub.6 H.sub.5                                                                              Oil                                 132       Me               p-ClC.sub.6 H.sub.4                                                                          88-90°                       133       Me               2,4-diClC.sub.6 H.sub.3                                                                      77-81°                       134       Me               p-FC.sub.6 H.sub.4                                 135       Me               o-ClC.sub.6 H.sub.4                                136       Me               o-FC.sub.6 H.sub.4                                 137       Me               o-MeC.sub.6 H.sub.4                                138       Me               2,4-diMeC.sub.6 H.sub.3                            139       Et               C.sub.6 H.sub.5                                                                              96-97°                       140       Et               p-ClC.sub.6 H.sub.4                                                                          105-106°                     141       Et               2,4-diClC.sub.6 H.sub.3                            142       Et               p-FC.sub.6 H.sub.4                                                                           94°                          143       Et               o-ClC.sub.6 H.sub.4                                144       Et               o-FC.sub.6 H.sub.4                                 145       Me               o-MeC.sub.6 H.sub.4                                146       Me               2,4-diMeC.sub.6 H.sub.3                            147       n-Pr             C.sub.6 H.sub.5                                                                              77-79°                       148       n-Pr             p-ClC.sub.6 H.sub.4                                149       n-Pr             p-FC.sub.6 H.sub.4                                 150       n-Pr             2,4-diClC.sub.6 H.sub.3                            151       n-Pr             o-ClC.sub.6 H.sub.4                                152       n-Pr             o-FC.sub.6 H.sub.4                                 153       n-Pr             o-MeC.sub.6 H.sub.4                                154       n-Pr             2,4-diMeC.sub.6 H.sub.3                            155       n-Pr             p-MeOC.sub.6 H.sub.4                               156       n-Pr             o-MeOC.sub.6 H.sub.4                               157       i-Pr             C.sub.6 H.sub.5                                    158       i-Pr             p-ClC.sub.6 H.sub.4                                159       i-Pr             p-FC.sub.6 H.sub.4                                 160       i-Pr             2,4-diClC.sub.6 H.sub.3                            161       i-Pr             o-ClC.sub.6 H.sub.4                                162       i-Pr             o-FC.sub.6 H.sub.4                                 163       i-Pr             o-MeC.sub.6 H.sub.4                                164       i-Pr             2,4-diMeC.sub.6 H.sub.3                            165       i-Pr             o-MeOC.sub.6 H.sub.4                               166       i-Pr             p-MeOC.sub.6 H.sub.4                               167       C.sub.3 H.sub.5  C.sub.6 H.sub.5                                                                              91-92°                       168       C.sub.3 H.sub.5  p-ClC.sub.6 H.sub.4                                                                          Oil                                 169       C.sub.3 H.sub.5  p-FC.sub.6 H.sub.4                                 170       C.sub.3 H.sub. 5 2,4-diClC.sub.6 H.sub.3                            171       C.sub.3 H.sub.5  o-ClC.sub.6 H.sub.4                                172       C.sub.3 H.sub.5  o-FC.sub.6 H.sub.4                                 173       C.sub.3 H.sub.5  o-MeC.sub.6 H.sub.4                                174       C.sub.3 H.sub.5  2,4-diMeC.sub.6 H.sub.3                            175       C.sub.3 H.sub.5  o-MeOC.sub.6 H.sub.4                               176       C.sub.3 H.sub.5  p-MeOC.sub.6 H.sub.4                                                                         101-2°                       177       n-Bu             C.sub.6 H.sub.5                                                                              62-63°                       178       n-Bu             p-FC.sub.6 H.sub.4                                                                           93-95°                       179       n-Bu             2,4-diClC.sub.6 H.sub.3                                                                      106-108°                     180       n-Bu             o-ClC.sub.6 H.sub.4                                181       n-Bu             o-FC.sub.6 H.sub.4                                 182       n-Bu             o-Me-C.sub.6 H.sub.4                               183       n-Bu             2,4-diMeC.sub.6 H.sub.3                            184       n-Bu             o-MeOC.sub.6 H.sub.4                               185       n-Bu             p-MeOC.sub.6 H.sub.4                               186       i-Bu             p-ClC.sub.6 H.sub.4                                187       i-Bu             p-FC.sub.6 H.sub.4                                 188       i-Bu             2,4-diClC.sub.6 H.sub.3                            189       i-Bu             o-ClC.sub.6 H.sub.4                                190       i-Bu             o-FC.sub.6 H.sub. 4                                191       i-Bu             o-MeC.sub.6 H.sub.4                                192       i-Bu             2,4-diMeC.sub.6 H.sub.3                            193       i-Bu             p-MeOC.sub.6 H.sub.4                               194       i-Bu             o-MeOC.sub.6 H.sub.4                               195       t-Bu             C.sub.6 H.sub.5                                                                              75°                          196       t-Bu             p-ClC.sub.6 H.sub.4                                                                          70-73°                       197       t-Bu             2,4-diClC.sub.6 H.sub.3                            198       t-Bu             p-FC.sub.6 H.sub.4                                                                           92-3°                        199       t-Bu             o-ClC.sub.6 H.sub.4                                200       t-Bu             o-FC.sub.6 H.sub.4                                 201       t-Bu             o-MeC.sub.6 H.sub.4                                202       t-Bu             2,4-diMeC.sub.6 H.sub.3                            203       t-Bu             o-MeOC.sub.6 H.sub.4                               204       t-Bu             p-MeOC.sub.6 H.sub.4                                                                         48°                          205       n-Pe             C.sub.6 H.sub.5                                    206       n-Pe             p-ClC.sub.6 H.sub.4                                207       n-Pe             2,4-diClC.sub.6 H.sub.3                            208       n-Pe             p-FC.sub.6 H.sub.4                                 209       n-Pe             o-ClC.sub.6 H.sub.4                                210       n-Pe             o-FC.sub.6 H.sub.4                                 211       n-Pe             o-MeC.sub.6 H.sub.4                                212       n-Pe             2,4-diMeC.sub.6 H.sub.3                            213       n-Pe             o-MeOC.sub.6 H.sub.4                               214       n-Pe             p-MeOC.sub.6 H.sub. 4                              215       C.sub.5 H.sub.9  C.sub.6 H.sub.5                                    216       C.sub.5 H.sub.9  p-ClC.sub.6 H.sub.4                                217       C.sub.5 H.sub.9  2,4-diClC.sub.6 H.sub.3                            218       C.sub.5 H.sub.9  p-FC.sub.6 H.sub.4                                 219       C.sub.5 H.sub.9  o-ClC.sub.6 H.sub.4                                220       C.sub.5 H.sub.9  o-FC.sub.6 H.sub.4                                 221       C.sub.5 H.sub.9  o-MeC.sub.6 H.sub.4                                222       C.sub.5 H.sub.9  p-MeC.sub.6 H.sub.4                                223       C.sub.5 H.sub.9  o-MeOC.sub.6 H.sub.4                               224       C.sub.5 H.sub.9  p-MeOC.sub.6 H.sub.4                               225       n-He             C.sub.6 H.sub.5                                    226       n-He             p-ClC.sub.6 H.sub.4                                227       n-He             2,4-diClC.sub.6 H.sub.3                            228       n-He             p-FC.sub.6 H.sub.4                                                                           97-99°                       229       n-He             o-ClC.sub.6 H.sub.4                                230       n-He             o-FC.sub.6 H.sub.4                                 231       n-He             o-MeC.sub.6 H.sub.4                                232       n-He             2,4-diMeC.sub.6 H.sub.3                            233       n-He             o-MeOC.sub.6 H.sub.4                               234       n-He             p-MeOC.sub.6 H.sub.4                               235       C.sub.6 H.sub.11 C.sub.6 H.sub.5                                                                              110-111°                     236       C.sub.6 H.sub.11 p-ClC.sub.6 H.sub.4                                                                          45°                          237       C.sub.6 H.sub.11 2,4-diClC.sub.6 H.sub.4                            238       C.sub.6 H.sub.11 p-FC.sub.6 H.sub.4                                 239       C.sub.6 H.sub.11 o-ClC.sub.6 H.sub.4                                240       C.sub.6 H.sub.11 o-FC.sub.6 H.sub.4                                 241       C.sub.6 H.sub.11 o-MeC.sub.6 H.sub.4                                242       C.sub.6 H.sub.11 2,4-diMeC.sub.6 H.sub.3                            243       C.sub.6 H.sub.11 o-MeOC.sub.6 H.sub.4                               244       C.sub.6 H.sub.11 p-MeOC.sub.6 H.sub.4                                                                         92-4°                        245       t-Bu             2-F4-MeOC.sub.6 H.sub.3 CH.sub.2                   246       t-Bu             2-MeO4-FC.sub.6 H.sub.3 CH.sub.2                   247       t-Bu             2-MeO4-ClC.sub.6 H.sub.3 CH.sub.2                  248       t-Bu             p-MeOC.sub.6 H.sub.4 CH.sub.2                                                                130-131°                     249       t-Bu             p-CF.sub.3C.sub.6 H.sub.4 CH.sub.2                 250       3-NO.sub.2 4-ClC.sub.6 H.sub.3                                                                 C.sub.6 H.sub.5                                                                              139-141                             251       m-ClC.sub.6 H.sub.4                                                                            C.sub.6 H.sub.5                                                                              108-110                             252       m-FC.sub.6 H.sub.4                                                                             p-ClC.sub.6 H.sub.4                                                                          55-59                               253       m-FC.sub.6 H.sub.4                                                                             p-FC.sub.6 H.sub.4                                                                           116-118                             254       p-OCH.sub.3 C.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                              88-89                               255       p-OC.sub.6 H.sub.5C.sub.6 H.sub.4                                                              C.sub.6 H.sub.5                                                                              103-105                             256       o-OCH.sub.3C.sub.6 H.sub.4                                                                     p-OCH.sub.3C.sub.6 H.sub.4                                                                   133-134                             257       o-FC.sub.6 H.sub.4                                                                             p-OCH.sub.3C.sub.6 H.sub.4                                                                   144-145                             258       p-NO.sub.2C.sub.6 H.sub.4                                                                      p-ClC.sub.6 H.sub.4                                                                          157-158                             259       p-OCH.sub.3C.sub.6 H.sub.4                                                                     p-ClC.sub.6 H.sub.4                                                                          105-106                             260       p-OC.sub.6 H.sub.5C.sub.6 H.sub.4                                                              o-ClC.sub.6 H.sub.4                                                                          100-102                             261       p-OC.sub.6 H.sub.5C.sub.6 H.sub.4                                                              o-FC.sub.6 H.sub.4                                                                           132-133                             262       o,p-diClC.sub.6 H.sub.3                                                                        p-OCH.sub.3C.sub.6 H.sub.4                                                                   178-180                             263       p-OCH.sub.3C.sub.6 H.sub.4                                                                     p-FC.sub.6 H.sub.4                                                                           124-125                             264       p-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4                                                           o,pdiClC.sub.6 H.sub.3                                                                       125-126                             265       p-CO.sub.2 MeC.sub.6 H.sub.4                                                                   C.sub.6 H.sub.5                                                                              70-72                               266       p-CNC.sub.6 H.sub.4                                                                            C.sub.6 H.sub.5                                                                              82-85                               267       p-CH.sub.3C.sub.6 H.sub.4                                                                      p-ClC.sub.6 H.sub.4                                                                          134-135                             268       p-CH.sub.3C.sub.6 H.sub.4                                                                      p-FC.sub.6 H.sub.4                                                                           124-125                             269       o-OCH.sub.3C.sub.6 H.sub.4                                                                     2,4-diClC.sub.6 H.sub.3                                                                      152-153                             270       p-OC.sub.6 H.sub.5C.sub.6 H.sub.4                                                              p-ClC.sub.6 H.sub.4                                                                          gum HCl                                                                       salt m.p.                                                                     177-178                             271       p-OC.sub.6 H.sub.5C.sub.6 H.sub.4                                                              p-FC.sub.6 H.sub.4                                                                           138-140                                                                       HCl salt                                                                      m.p. 171-173                        272       p-OCH(CH.sub.3).sub.2C.sub.6 H.sub.4                                                           p-ClC.sub.6 H.sub.4                                                                          151-153                             273       n-Bu             p-CH.sub.3C.sub.6 H.sub.4                                                                    80-81                               274       n-He             p-CH.sub.3C.sub.6 H.sub.4                                                                    76-78                               275       4-OCF.sub.3C.sub.6 H.sub.4                                                                     2-FC.sub.6 H.sub.4                                                                           glass                               276       "                4-FC.sub.6 H.sub.4                                                                           132-133                             277       "                2-OCH.sub.3C.sub.6 H.sub.4                                                                   115-116                             278       2-OCF.sub.2 HC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                          114-115                             279       2-OCF.sub.2 CF.sub.2 HC.sub.6 H.sub.4                                                          4-FC.sub.6 H.sub.4                                                                           115-116                             280       4-OCF.sub.2 CF.sub.2 HC.sub.6 H.sub.4                                                          "              125-126                             281       "                2-FC.sub.6 H.sub.4                                                                           110-111                             282                                                                                      ##STR4##        4-ClC.sub.6 H.sub.4                                                                          129-130                             283       2,4-diClC.sub.6 H.sub.3                                                                         -n-C.sub.3 H.sub.7 (CH.sub.3)CH.CH.sub.2                                                     ##STR5##                           284       2-ClC.sub.6 H.sub.4                                                                            4-OC.sub.2 H.sub.5C.sub.6 H.sub.4                                                            94-96                               285       2,4-diClC.sub.6 H.sub.3                                                                        4-OC.sub.2 H.sub.5C.sub.6 H.sub.4                                                            159-161                             286       4-ClC.sub.6 H.sub.4                                                                            4-NH.sub.2C.sub.6 H.sub.4                                                                    56                                  287       4-Cl C.sub.6 H.sub.4                                                                           4-CH.sub.3 CONHC.sub.6 H.sub.4                                                               70-75                               288       4-ClC.sub.6 H.sub.4                                                                            4-CNC.sub.6 H.sub.4                                                                          160                                 289       4-FC.sub.6 H.sub.4                                                                             4-CNC.sub.6 H.sub.4                                                                          139-140                             290       4-CH.sub.3C.sub.6 H.sub.4                                                                      2,4-diClC.sub.6 H.sub.3                                                                      183                                 291       2-ClC.sub.6 H.sub.4                                                                            2-OCH.sub.3C.sub.6 H.sub.4                                                                   148-150                             292       4-CNC.sub.6 H.sub.4                                                                            2,4-diClC.sub.6 H.sub.3                                                                      182-184                             293       2-F4-OCH.sub.3C.sub.6 H.sub.3                                                                  4-FC.sub.6 H.sub.4                                                                           161-162                             294       2-Cl4-OCH.sub.3C.sub.6 H.sub.3                                                                 4-FC.sub.6 H.sub.4                                                                           138-140                             295       2-Cl4-OCH.sub.3C.sub.6 H.sub.3                                                                 4-ClC.sub.6 H.sub.4                                                                          176-177                             296       2-F4-OCH.sub.3C.sub.6 H.sub.3                                                                  2-ClC.sub.6 H.sub.4                                                                          170-172                             297       2-F4-OCH.sub.3C.sub.6 H.sub.3                                                                  4-ClC.sub.6 H.sub.4                                                                          134-136                             298       2-Cl4-CH.sub.3C.sub.6 H.sub.3                                                                  4-FC.sub.6 H.sub.4                                                                           158                                 299       2-CH.sub.34-ClC.sub.6 H.sub.3                                                                  4-FC.sub.6 H.sub.4                                                                           65-67                               300       2-F4-CH.sub.3C.sub.6 H.sub.3                                                                   4-FC.sub.6 H.sub.4                                                                           --                                  301       C.sub.4 H.sub.7  C.sub.6 H.sub.5                                                                              Oil                                 302       4-NO.sub.2C.sub.6 H.sub.4                                                                      4-NO.sub.2C.sub.6 H.sub.4                          303       4-NH.sub.2C.sub.6 H.sub.4                                                                      4-NH.sub.2C.sub.6 H.sub.4                          304        .sub.-s-butyl   2,4-diCl.sub.2C.sub.6 H.sub.3                      305        .sub.-s-butyl   4-ClC.sub.6 H.sub.4                                306       4-ClC.sub.6 H.sub.4                                                                            3-CH.sub.34-ClC.sub.6 H.sub.5                                                                175-176                             307       2,4-diClC.sub.6 H.sub.3                                                                        2,4-diClC.sub.6 H.sub.3                                                                      170                                 308       2-NO.sub.2C.sub.6 H.sub.4                                                                      3-NO.sub.2C.sub.6 H.sub.4                                                                    170-172                             309       4-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                             4-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                           gum                                 __________________________________________________________________________     *Includes 1 mole of ethanol occluded in the crystal lattice.                  .sup.+ Compounds 8 and 18 were obtained as polymorphs and this explains       their different melting points.                                               n-Pe = nPentyl                                                                 n-He = nhexyl                                                                C.sub.3 H.sub.5 = cyclopropyl                                                 C.sub.4 H.sub.7 = cyclobutyl                                                  C.sub.5 H.sub.9 = cyclopentyl                                                 C.sub.6 H.sub.11 = cyclohexyl                                                 MO = morpholino                                                               Z = difluoromethylenedioxy                                               

The compounds of general formula (I) may be produced by reacting acompound of general formula (II) or (III): ##STR6## in which R¹ and R²are as defined above and X is a halogen atom (preferably a chlorine orbromine atom), with 1,2,4-triazole either in the presence of anacid-binding agent or in the form of one of its alkali metal salts in aconvenient solvent. Suitably the compound of general formula (II) or(III) is reacted at 20°-100° C. with the sodium salt of 1,2,4-triazole(the salt can be prepared by adding either sodium hydride or sodiummethoxide to 1,2,4-triazole) in a convenient solvent such asacetonitrile, methanol, ethanol or dimethylformamide. The product can beisolated by pouring the reaction mixture into water and recrystallisingthe solid formed from a convenient solvent.

The compounds of general formula (II) and (III) can be prepared byreacting a compound of general formula (IVa) or (IVb): ##STR7## whereinR¹, R² and X are as defined above with, respectively, a Grignardcompound of general formula (Va) or (Vb): ##STR8## wherein R¹ and R² areas defined above and Y us a halogen (preferably chlorine, bromine oriodine) in a convenient solvent such as diethyl ether ortetrahydrofuran. Generally a mixture of the compounds of general formula(II) and (III) are obtained. For example, when a compound of generalformula (IVa) wherein R¹ is alkyl or cycloalkyl is reacted, the compoundof formula (II) generally predominates in the mixture; on the otherhand, when R¹ is optionally substituted phenyl, the compound of generalformula (III) generally predominates in the mixture.

The compounds of general formula (IV) and (V) may be made by methods setout in the literature.

The compounds of general formula (II) wherein each of R¹ and R², whichmay be the same or different, is substituted phenyl may also be preparedby reacting the appropriate benzophenone compound of general formula(VI)

    R.sup.1 --CO--R.sup.2

wherein R¹ and R² are as defined above, with dimethyl oxosulphoniummethylide (Corey and Chaykovsky JACS, 1965, 87, 1353-1364) or dimethylsulphonium methylide (Corey and Chaykovsky, JACS, 1962, 84, 3782) usingmethods set out in the literature.

The benzophenone compounds of general formula (VI) can be prepared,using the Friedel-Crafts reaction, by reacting a substituted benzoylchloride with the appropriately substituted benzene in the presence of aLewis acid e.g. aluminium chloride.

The compounds of general formula (II) wherein each of R¹ is alkyl,cycloalkyl or optionally substituted phenyl and R² is optionallysubstituted phenyl or optionally substituted benzyl can also be producedby reacting a β-hydroxy selenide compound of general formula (VII)##STR9## wherein R¹ and R² are as defined above, with methyl iodide inpotassium t-butoxide according to the method of Van Ende, Dumont andKrief, Angew. Chem. Int. Ed., 1975, 14, 700.

The β-hydroxy selenide compound can be prepared by treating thediselenide with the appropriate ketone in the presence of butyl lithium.

The compounds of general formula (III) wherein R¹ is alkyl or cycloalkyland R² is optionally substituted benzyl (particularly benzyl ringsubstituted with alkoxy) can also be prepared by reacting a compound ofgeneral formula (VIII) ##STR10## wherein R¹ and R² are as defined aboveand Ar is aryl (e.g. phenyl) with an alkylating agent to give thecorresponding sulphonium salt which is then reacted with 1,2,4-triazolein the form of an alkali metal (e.g. sodium or potassium) salt. Thecompound of general formula (VIII) can be prepared by methods known inthe art.

The invention further provides, as useful intermediates, the compoundshaving the formulae: ##STR11## wherein R¹ and R² are as defined in anyof the preceding claims and X is a halogen atom, especially chlorine.

In particular the invention provides a compound as defined above in thepreceding paragraph wherein R¹ and R², which may be the same ordifferent, are optionally substituted phenyl.

In a preferred aspect the invention provides as useful, novel,intermediates the compounds of formulae: ##STR12##

The salts and metal complexes of the compounds of general formula (I)can be prepared from the latter in known manner. For example, thecomplexes can be made by reacting the uncomplexed compound with a metalsalt in a suitable solvent.

The compounds of general formula (I) are generally prepared by the abovereactions in the form of racemic mixtures. The resolution of thesemixtures into the constituent enantiomers can be performed by knownmethods. Examples of these methods are (1) forming the diastereoisomericsalts or esters of the compound of general formula (I) with an opticallyactive acid (e.g. camphor sulphonic acid), separating the isomeric saltsor esters and converting the separated isomeric salts or esters into theenantiomers of the compound of general formula (I); (2) forming thediastereoisomeric carbamates of the compound of general formula (I) byreacting a halo-formate (e.g. chloroformate) of the latter with anoptically active amine (e.g. α-methylbenzylamine), separating theisomeric carbamates, and converting the separated isomeric carbamatesinto the enantiomers of the compound of general formula (I), reactingthe hemiphthate with an optically active amine (e.g.α-methylbenzylamine) to give a salt of the hemiphthate, separating theisomeric salts and converting the separated salts into the enantiomersof the compound of general formula (I); or (4) resolving the mixturesusing enantio-selective crystallisation techniques (Leigh, Chemistry andIndustry, 1970, pages 1016-1017, and ibid, 1977, page 36). Theseparation of the diastereoisomeric salts, esters and carbamates can beachieved by for example crystallisation techniques or by high pressureliquid chromatography (HPLC). Alternatively, the enantiomers can beprepared directly from the compound of general formula (II) bystereospecific reduction, for example by biochemical reduction (usingfor example yeast or Aspergillus niger) or by hydrogenation using chiralcatalysts (e.g. a Wilkinson's catalyst) or by reduction withborohydride/amino acid complexes.

The compounds, salts, andmetal complexes, are active fungicides,particularly against the diseases:

Piricularia oryzae on rice

Puccinia recondita, Puccinia striiformis and other rusts on wheat,Puccinia hordei, Puccinia striiformis and other rusts on barley, andrusts on other hosts e.g. coffee, apples, vegetables and ornamentalplants

Plasmopara viticola on vines

Erysiphe graminis (powdery mildew) on barley and wheat and other powderymildews on various hosts such as

Sphaerotheca fuliginea on cucurbits (e.g. cucumber), Podosphaeraleucotricha on apples and Uncinula necator on vines

Helminthosporium spp. and Rhynchosporium spp. on cereals

Cercospora arachidicola on peanuts and other Cercospora species on forexample sugar beet, bananas and soya beans

Botrytis cinerea (grey mould) on tomatoes, strawberries, vines and otherhosts

Phytophthora infestans (late blight) on tomatoes

Venturia inaequalis (scab) on apples

Some of the compounds have also shown a broad range of activitiesagainst fungi in vitro. They have activity against various post-harvestdiseases on fruit (e.g. Penicillium digatatum and italicum on orangesand Gloeosporium musarum on bananas). Further some of the compounds areactive as seed dressings against: Fusarium spp., Septoria spp., Tilletiaspp. (i.e. bunt, a seed borne disease of wheat), Ustilago spp.,Helminthosporium spp. on cereals, Rhizoctonia solani on cotton andCorticium sasakii on rice.

The compounds can move acropetally in the plant tissue. Moreover, thecompounds can be volatile enough to be active in the vapour phaseagainst fungi on the plant.

They may also be useful as industrial (as opposed to agricultural)fungicides, e.g. in the prevention of fungal attack on wood, hides,leather and especially paint films.

The compounds can also have plant growth regulating activities.

The plant growth regulating effects of the compounds are manifested asfor example a stunting or dwarfing effect on the vegetable growth ofwoody and herbaceous mono- and di-cotyledonous plants. Such stunting ordwarfing may be useful, for example, in peanuts, cereals and soya beanwhere reduction in stem growth may reduce the risk of lodging and mayalso permit increased amounts of fertiliser to be applied. The stuntingof woody species is useful in controlling the growth of undergrowthunder power lines etc. Compounds which induce stunting or dwarfing mayalso be useful in modifying the stem growth of sugar cane therebyincreasing the concentration of sugar in the cane at harvest; in sugarcane, the flowering and ripening may be controllable by applying thecompounds. Stunting of peanuts can assist in harvesting. Growthretardation of grasses can help maintenance of grass swards. Examples ofsuitable grasses are Stenotaphrum secundatum (St. Augustine grass),Cynosurus cristatus, Lolium multiflorum and perenne, Agrostis tenuis,Cynodon dactylon (Bermuda grass), Dactylis glomerata, Festuca spp. (e.g.Festuca rubra) and Poa spp. (e.g. Poa pratense). The compounds may stuntgrasses without significant phytotoxic effects and without deleteriouslyaffecting the appearance (particularly the colour) of the grass; thismakes such compounds attractive for use on ornamental lawns and on grassverges. They may also have an effect on flower head emergence in forexample grasses. The compounds can also stunt weed species present inthe grasses; examples of such weed species are sedges (e.g. Cyperusspp.) and dicotyledonous weeds (e.g. daisy, plantain, knotweed,speedwell, thistle, docks and ragwort). The growth of non-cropvegetation (e.g. weeds or cover vegetation) can be retarded thusassisting in the maintenance of plantation and field crops. In fruitorchards, particularly orchards subject to soil erosion, the presence ofgrass cover is important. However excessive grass growth requiressubstantial maintenance. The compounds of the invention could be usefulin this situation as they could restrict growth without killing theplants which would lead to soil erosion; at the same time the degree ofcompetition for nutrients and water by the grass would be reduced andthis could result in an increased yield of fruit. In some cases, onegrass species may be stunted more than another grass species; thisselectivity could be useful for example for improving the quality of asward by preferential suppression of the growth of undesirable species.

The dwarfing may also be useful in miniaturising ornamental, household,garden and nursery plants (e.g. poinsettias, chrysanthemums, carnations,tulips and daffodils).

As indicated above, the compounds can also be used to stunt woodyspecies. This property can be used to control hedgerows or to shapefruit trees (e.g. apples). Some coniferous trees are not significantlystunted by the compounds so the compounds could be useful in controllingundesirable vegetation in conifer nurseries.

The plant growth regulating effect may (as implied above) manifestitself in an increase in crop yield.

In the potato, vine control in the field and inhibition of sprouting inthe store may be possible.

Other plant growth regulating effects caused by the compounds includealteration of leaf angle and promotion of tillering in monocotyledonousplants. The former effect may be useful for example in altering the leaforientation of, for example, potato crops thereby letting more lightinto the crops and inducing an increase in phytosynthesis and tuberweight. By increasing tillering in monocotyledonous crops (e.g. rice),the number of flowering shoots per unit area may be increased therebyincreasing the overall grain yield of such crops. In grass swards anincrease in tillering could lead to a denser sward which may result inincreased resilience in wear.

The treatment of plants with the compounds can lead to the leavesdeveloping a darker green colour.

The compounds may inhibit, or at least delay, the flowering of sugarbeet and thereby may increase sugar yield. They may also reduce the sizeof sugar beet without reducing significantly the sugar yield therebyenabling an increase in planting density to be made. Similarly in otherroot crops (e.g. turnip, swede, mangold, parsnip, beetroot, yam andcassava) it may be possible to increase the planting density.

The compounds could be useful in restricting the vegetative growth ofcotton thereby leading to an increase in cotton yield.

The compounds may be useful in rendering plants resistant to stresssince the compounds can delay the emergence of plants grown from seed,shorten stem height and delay flowering; these properties could beuseful in preventing frost damage in countries where there issignificant snow cover in the winter since then the treated plants wouldremain below snow cover during the cold weather. Further the compoundsmay cause drought or cold resistance in certain plants.

When applied as seed treatments at low rates the compounds can have agrowth stimulating effect on plants.

In carrying out the plant growth regulating method of the invention, theamount of compound to be applied to regulate the growth of plants willdepend upon a number of factors, for example the particular compoundselected for use, and the identity of the plant species whose growth isto be regulated. However, in general an application rate of 0.1 to 15,preferably 0.1 to 5, kg per hectare is used. However, on certain plantseven application rates within these ranges may give undesired phytotoxiceffects. Routine tests may be necessary to determine the best rate ofapplication of a specific compound for any specific purpose for which itis suitable.

The compounds may be used as such for fungicidal or plant growthregulating purposes but are more conveniently formulated intocompositions for such usage. The invention thus provides also afungicidal or plant growth regulating composition comprising a compoundwhich is an enantiomer of the invention or an ester, salt or complexthereof, and a carrier or diluent.

The invention also provides a method of combating fungi, which comprisesapplying to a plant, to seed of a plant or to the locus of a plant orseed, a compound which is an enantiomer of the invention or an ester,salt or complex thereof.

The invention also provides a method of regulating plant growth whichcomprises applying to a plant, to seed of a plant or to the locus of aplant or seed, a compound which is an enantiomer of the invention or anester, salt or complex thereof as hereinbefore defined.

The compounds can be applied in a number of ways, for example they canbe formulated or unformulated, directly to the foliage of a plant, toseeds or to other medium in which plants are growing or are to beplanted, or they can be sprayed on, dusted on or applied as a cream orpaste formulation, or they can be applied as a vapour. Application canbe to any part of the plant, bush or tree, for example to the foliage,stems, branches or roots, or to soil surrounding the roots, or to theseed before it is planted.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal method of the invention includespreventative, protectant, prophylactic and eradicant treatment.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dusting powders or granulescomprising the active ingredient and a solid diluent or carrier, forexample fillers such as kaolin, bentonite, kieselguhr, dolomite, calciumcarbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt'searth, diatomaceous earth and China clay. Such granules can be preformedgranules suitable for application to the soil without further treatment.These granules can be made either by impregnating pellets of filler withthe active ingredient or by pelleting a mixture of the active ingredientand powdered filler. Compositions for dressing seed, for example, maycomprise an agent (for example a mineral oil) for assisting the adhesionof the composition to the seed; alternatively the active ingredient canbe formulated for seed dressing purposes using an organic solvent (forexample N-methylpyrrolidone or dimethylformamide).

The compositions may also be in the form of dispersible powders,granules or grains comprising a wetting agent to facilitate thedisperion in liquids of the powder or grains which may contain alsofillers and suspending agents.

The aqueous dispersions or emulsions may be prepared by dissolving theactive ingredient(s) in an organic solvent optionally containingwetting, dispersing or emulsifying agent(s) and then adding the mixtureto water which may also contain wetting, dispersing or emulsifyingagent(s). Suitable organic solvents are ethylene dichloride, isopropylalcohol, propylene glycol, diacetone alcohol, toluene, kerosene,methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol,tetrahydrofurfuryl alcohol, and glycol ethers (e.g. 2-ethoxyethanol and2-butoxyethanol).

The compositions to be used as sprays may also be in the form ofaerosols wherein the formulation is held in a container under pressurein the presence of a propellant, e.g. fluorotrichloromethane ordichlorodifluoromethane.

The compounds can be mixed in the dry state with a pyrotechnic mixtureto form a composition suitable for generating in enclosed spaces a smokecontaining the compounds.

Alternatively, the compounds may be used in a microencapsulated form.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The compounds can be used as mixtures with fertilisers (e.g. nitrogen-,potassium- or phosphorous-containing fertilisers). Compositionscomprising only granules of fertiliser incorporating, for example coatedwith, the compound, are preferred. Such granules suitably contain up to25% by weight of the compound. The invention therefore also provides afertiliser composition comprising a compound as hereinbefore defined.

The compositions may also be in the form of liquid preparations for useas dips or sprays which are generally aqueous dispersions or emulsionscontaining the active ingredient in the presence of one or moresurfactants e.g. wetting agent(s), dispersing agent(s), emulsifyingagent(s) or suspending agent(s). These agents can be cationic, anionic,or non-anionic agents. Suitable cationic agents are quaternary ammoniumcompounds, for example cetyltrimethylammonium bromide.

Suitable anionic agents are soaps, salts of aliphatic monoesters ofsulphuric acid (for example sodium lauryl sulphate), and salts ofsulphonated aromatic compounds (for example sodiumdodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate,butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- andtriisopropyl-naphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octyl- or nonyl-phenol and octylcresol. Other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, the condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending agents arehydrophilic colloids (for example polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and the vegetable gums (for example gum acaciaand gum tragacanth).

The compositions for use as aqueous dispersions or emulsions aregenerally supplied in the form of a concentrate containing a highproportion of the active ingredient(s), the concentrate to be dilutedwith water before use. These concentrations often should be able towithstand storage for prolonged periods and after such storage becapable of dilution with water in order to form aqueous preparationswhich remain homogenous for a sufficient time to enable them to beapplied by conventional spray equipment. The concentrates mayconveniently contain up to 95%, suitably 10-85%, for example 25-60%, byweight of the active ingredient(s). These concentrates suitably containorganic acids (e.g. alkaryl or aryl sulphonic acids such asxylene-sulphonic acid or dodecylbenzenesulphonic acid) since thepresence of such acids can increase the solubility of the activeingredient(s) in the polar solvents often used in the concentrates. Theconcentrates suitably contain also a high proportion of surfactants sothat sufficiently stable emulsions in water can be obtained. Afterdilution to form aqueous preparations, such preparations may containvarying amounts of the active ingredient(s) depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient(s) may be used.

The compositions of this invention can comprise also other compound(s)having biological activity, e.g. compounds having similar orcomplementary fungicidal or plant growth regulating activity orcompounds having herbicidal or insecticidal activity.

The other fungicidal compound can be for example one which is capable ofcombating ear diseases of cereals (e.g. wheat) such as Septoria,Gibberella and Helminthosporium spp., seed and soil borne diseases anddowny and powdery mildews on grapes and powdery mildew and scab on appleetc. These mixtures of fungicides can have a broader spectrum ofactivity than the compound of general formula (I) alone; further theother fungicide can have a synergistic effect on the fungicidal activityof the compound of the general formula (I). Examples of the otherfungicidal compound are imazalil, benomyl, carbendazim,thiophanate-methyl, captafol, captan, sulphur, triforine, dodemorph,tridemorph, pyrazophos, furalaxyl, ethirimol, dimethirimol, bupirimate,chlorothalonil, vinclozolin, procymidone, iprodione, metalaxyl,fosetyl-aluminium, carboxin, oxycarboxin, fenarimol, nuarimol, fenfuram,methfuroxam, nitrotalisopropyl, triadimefon, thiabendazole, etridiazole,triadimenol, biloxazol, dithianon, binapacryl, quinomethionate,quazatine, dodine, fentin acetate, fentin hydroxide, dinocap, folpet,diclofluanid, ditalimphos, kitazin, fenpropemorph, cycloheximide,dichlobutrazol, a dithiocarbamate, a copper compound, a mercurycompound, DPX 3217, RH 2161, Chevron RE 20615, CGA 64250, CGA 54251 andRO 14-3169.

The compounds of general (I) can be mixed with soil, peat or otherrooting media for the protection of plants against seed-borne,soil-borne or foliar fungal diseases.

Suitable insecticides are pirimor, croneton, dimethoate, metasystox andformothion.

The other plant growth regulating compound can be one which controlsweeds or seedhead formation, improves the level or longevity of theplant growth regulating activity of the compounds of general formula(I), selectively controls the growth of the less desirable plants (e.g.grasses) or causes the compound of general formula (I) to act faster orslower as a plant growth regulating agent. Some of the other agents willbe herbicides. Examples of suitable agents are the gibberellins (e.g.GA₃, GA₄ or GA₇), the auxins (e.g. indoleacetic acid, indolebutyricacid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g.kinetin, diphenylurea, benzimidazole, benzyladenine or BAP),phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoic acids(e.g. TIBA), morphactins (e.g. chlorfluorecol), maleic hydrazide,glyphosate, glyphosine, long chain fatty alcohols and acids (e.g. OffShoot O or Off Shoot T), dikegulac, Sustar, Embark, substitutedquaternary ammonium and phosphonium compounds (e.g. CCC or Phosfon-D),Ethrel, carbetamide, Racuza, Alar, asulam, abscissic acid, isopyrimol,RH531, hydroxybenzonitriles (e.g. bromoxynil), Avenge, Suffix, Lontrelor thiocarbamates (e.g. Eptam).

The following Examples illustrate the invention; the temperatures aregiven in degrees Centigrade (°).

EXAMPLE 1

This Example illustrates the preparation of:1-(1,2,4-Triazol-1-yl)-2,3-diphenyl-propan-2-ol (Compound No 1 of TableI).

Benzyl chloride (0.2 mol) was dissolved in dry diethyl ether (200 ml)and added dropwise to magnesium turnings (0.22 g atoms). After all themagnesium had reacted, the solution was refluxed for 1 hour and cooledto room temperature. Phenacyl chloride (0.1 mol) in dry diethyl ether(100 ml) was added dropwise over 1 hour at such a rate as to maintaingentle reflux. The solution was then refluxed for 2 hours, and cooled toroom temperature; the mixture was poured into ice and the complexdecomposed with ammonium chloride solution. The ethereal solution waswashed several times with water (2×200 ml), dried (Na₂ SO₄), and thesolvent removed in vacuo to give, as a colourless oil, the crudechlorohydrin which was dissolved in dimethyl formamide (80 ml) and asolution of sodium triazole [prepared from sodium (0.1 g atoms) inmethanol (40 ml) and 1,2,4-triazole (0.1 mol)] added dropwise at roomtemperature. After stirring at room temperature for 2 hours, thesolution was warmed at 50° for 3 hours. The solvent was removed in vacuoand the residue poured into water to give a crystalline solid which wasrecrystallised from ethanol/petroleum ether to give the title compound,m.p. 124.5°.

EXAMPLE 2

This Example illustrates the preparation of:1-(1,2,4-Triazol-1-yl)-2-phenyl-3-p-fluorophenyl-propan-2-ol (CompoundNo 3 of Table I).

p-Fluorobenzyl chloride (0.1 mol) in dry diethyl ether (100 ml) wasadded dropwise to magnesium turnings (0.11 g atoms) and the solution wasstirred vigorously until refluxing occurred. When all the magnesium hadreacted, the solution was refluxed for a further 1 hour and then cooledto room temperature. Phenacyl chloride (0.05 mol) in dry diethyl ether(50 ml) was added dropwise to the solution over 1 hour at such a rate asto maintain gentle reflux. The mixture was refluxed for 2 hours, cooledto room temperature and the mixture poured into ice/ammonium chloridesolution to decompose the complex. The ethereal solution was washedseveral times with water (2×200 ml), dried (Na₂ SO₄), and the solventremoved in vacuo to give, as a colourless oil, the crude chlorohydrin.The latter was dissolved in dimethyl-formamide (40 ml) and a solution ofsodium triazole [prepared from sodium (0.05 g atoms) in methanol (20 ml)and 1,2,4-triazole (0.05 mol)] added dropwise at room temperature. Afterstirring at room temperature for 2 hours, the solution was warmed at 50°for 3 hours. The solvent was removed in vacuo and the mixture pouredinto water to give a crystalline solid which was recrystallised frompetroleum ether/chloroform to give the title compound, m.p. 116-8°.

EXAMPLE 3

This Example illustrates the preparation of:1,1-Diphenyl-2-(1,2,4-triazol-1-yl)-ethan-1-ol (Compound No 17 of TableI).

Stage 1. Bromobenzene (0.2 mol, 31.4 g) in sodium dry diethyl ether (200ml) was added dropwise to magnesium (0.22 gram atoms, 5.3 g). After allthe magnesium had reacted, phenacyl chloride (0.1 mol, 15.5 g) indiethyl ether (100 ml) was added dropwise to the solution stirred atroom temperature for 1 hour. The reaction mixture was poured intosaturated ammonium chloride solution, washed with water (3×150 ml), anddried (Na₂ SO₄). Removal of the ether gave a pale yellow oil whichsolidified on standing. Recrystallisation from the petroleum ether(60°-80°) gave 1,1-diphenyl-2-chloro-ethan-1-ol (60%) as a whitecrystalline solid, m.p. 56°-57°.

Stage 2. 1,2,4-Triazole (0.03 mol, 2.07 g) was added portionwise to asuspension of sodium hydride (0.03 mol, 0.72 g) in DFM (30 ml) and thesolution stirred until effervescence ceased.1,2-Diphenyl-2-chloro-ethan-1-ol (0.015 mol, 2.94 g) indimethylformamide (DMF; 10 ml) was added dropwise and the solutionwarmed at 100° for six hours. The reaction mixture was poured into waterand a white solid crystallised out. This was filtered off, washed withwater, dried, and recrystallised from ethanol to give the title compoundas a white crystalline solid, m.p. 128°-129°.

EXAMPLE 4

This Example illustrates the preparation of:2-Methyl-4-phenyl-5-(1,2,4-triazol-1-yl)-pentan-4-ol (Compound No 31 ofTable I).

Stage 1. The Grignard reagent generated from isobutyl bromide (0.1 mol,13.7 g) in sodium dry diethyl ether (50 ml) and magnesium turnings (0.11g atoms; 2.6 g) was added dropwise to a solution of phenacyl chloride(0.05 mol, 7.7 g) in sodium dry diethyl ether (100 ml) so that gentlereflux was maintained. The solution was then stirred at room temperaturefor 1 hour and the magnesium complex destroyed by pouring into asaturated ammonium chloride solution (200 ml). The ethereal extract waswashed with water (3×150 ml) and dried (Na₂ SO₄). Removal of the solventgave a colourless liquid which distilled at reduced pressure to give2-methyl-4-phenyl-5-chloro-pentan-4-ol (70%), b.p. 86°-88°/0.01 mm Hg.

Stage 2. 1,2,4-Triazole (0.03 mol, 2.07 g) was added portionwise in 100%sodium hydride (0.03 mol, 0.72 g) in dry DMF (30 ml) and stirred at roomtemperature until the effervescence ceased.2-Methyl-4-phenyl-5-chloro-pentan-4-ol (0.01 mol, 2.1 g) in dry DMF 10ml) was added dropwise at room temperature and then the solution wasstirred at 100° l for 6 hours. On cooling to room temperature thesolution was poured into water to precipitate out a solid which wasrecrystallised from petroleum (60°-80°)/chloroform giving the titlecompound (60%) as a white crystalline solid, m.p. 94°-95°.

EXAMPLE 5

1-(1,2,4-Triazol-1-yl)-2-o-chlorophenyl-2-p-fluorophenyl-ethan-2-ol(Compound No 45 of Table I).

A solution of dimethyl oxosulphonium methylide was prepared undernitrogen from sodium hydride (0.03 mol) and powdered trimethyloxosulphonium iodide (0.03 mol) in dry dimethylsulphoxide (DMSO; 30 ml).A solution of o-chlorophenyl p-fluorophenyl ketone (0.025 mol) in DMSO(10 ml) was added dropwise at room temperature. The solution was thenheated at 50° for 1.5 hours, cooled to room temperature and poured intowater. The solution was extracted with diethyl ether (100 ml), washedwith water (3×100 ml), and dried over anhydrous sodium sulphate. Removalof the solvent gave 1-o-chlorophenyl-1-p-fluorophenyl ethylene oxide(90%) as a colourless liquid.

1,2,4-Triazole (0.04 mol) was added portionwise to sodium hydride (0.04mol) in DMF (40 ml) and the solution stirred at room temperature untileffervescence ceased. 1-o-Chlorophenyl-1-p-fluorophenyl ethylene oxide(0.02 mol) in DMF (10 ml) was added dropwise and the solution stirred at80° for 4 hours. The solution was poured into water and triturated withpetroleum ether to give a white crystalline solid which was filtered offand dried. Recrystallisation from petroleum ether (60°-80°)/methylenechloride gave the title compound (70%) as a white crystalline solid,m.p. 115°-116°.

EXAMPLE 6

This Example illustrates the preparation of:2,2-Dimethyl-3-(2-methoxybenzyl)-4-(1,2,4-triazol-1-yl)-butan-3-ol(Compound No 130 of Table I).

Stage 1. Potassium t-butoxide (19 g) was dissolved in dimethylsulphoxide(200 ml; dried by distilling from calcium hydride and sodamide) andpinacolone (15 g; freshly distilled from calcium hydride) was addedunder argon to give a yellow solution. o-Methoxyphenyl iodide (10 g) wasthen added and a brown colour rapidly developed. The solution wasstirred for 1.5 hours before pouring into water (1 liter), acidifyingthe mixture with 2M hydrochloric acid and extracting it with diethylether. Evaporation of the dried (MgSO₄) ethereal solution gave a yellowliquid (11.8 g) b.p. 88°-93° C./0.9 mm. The distillate solidified togive 2,2-dimethyl-4-(o-methoxy-phenyl)butan-3-one (6 g).

Stage 2. Thioanisole (3.3 g) was added to diazobicyclooctane (3.5 g) indry tetrahydrofuran (THF) under argon and the colourless solution wascooled in an ice/salt bath. 1.6M-butyl lithium solution (20 ml) inhexane was then added over 10 minutes at 0° to 2° C. After stirring theyellow solution for 15 minutes, a solid was precipitated. The mixturewas stirred for a further 45 minutes in the ice bath and then it wasallowed to warm up to room temperature. The mixture was then cooled inthe ice bath and a solution of the product (5 g) of stage 1 in dry THF(25 ml) was added at 0° to 5° C. When the addition was complete, theresultant yellow solution was allowed to stand overnight, poured intowater, acidified with 2M-hydrochloric acid and extracted with diethylether. The ethereal solution was washed well with water, dried (MgSO₄)and evaporated to give a yellow liquid (8.8 g) which solidified onstanding. Recrystallisation from petroleum ether (60°-80°) gave2,2-dimethyl-3-hydroxy-3-(o-methoxybenzyl)-4-thiophenylbutane (3.1 g),m.p. 74°-75° C.

Stage 3. The product (2.5 g) of Stage 2 was added to a stirredsuspension of trimethyl oxonium tetrafluoroborate (1.3 g) in methylenechloride (25 ml). After about 1 hour a clear solution was obtained. Thesolvent was then removed on the rotavaporator to give a pale organe gum,which was dissolved in dry DMF (10 ml) and the solution added to asolution of 1,2,4-triazole sodium salt (1.2 g) in DMF (15 ml). [Thesolution was prepared by washing sodium hydride with dry diethyl ether,suspending it in dry DMF and adding the triazole]. The reaction mixturewas then stirred at 120° C. for 2.5 hours. The reaction mixture was thenquenched by pouring into water (100 ml) and the emulsion was extractedwith diethyl ether (3×50 ml). The ethereal solution was washed well withwater, dried (MgSO₄) and evaporated to give a pale yellow liquid. Themixture was subjected to dry column chromatography on silica elutingwith diethyl ether to give a colourless liquid which solidified ontrituration with diethyl ether. Recrystallation from petroleum ether(60°-80°) gave the title compound (0.5 g; 23%), m.p. 113°-116°.

EXAMPLE 7

This Example illustrates the preparation of:1-(1,2,4-Triazol-1-yl)-2-(2-chloro-4-methoxy-phenyl)-2-(4-fluoro-phenyl)-ethan-2-ol(Compound No 294 of Table I).

Stage 1. 3-chloroanisole (0.1 mol) was added dropwise to a suspension ofaluminium chloride (0.11 ml) in carbon disulphide (40 ml) at roomtemperature and stirred for 30 minutes until it had dissolved. Themixture was cooled in ice and 4-fluorobenzoyl chloride (0.1 mol) addeddropwise. After complete addition the solution was stirred for 1 hour atroom temperature and refluxed for 1 hour. The solution was poured intoice (200 ml), containing CHCl (20 ml), extracted with ether (200 ml),washed with water (3×150 ml), and dried over anhydrous sodiumsulphonate. Removal of the solvent gave an oil which was purified bycolumn chromatography silica K6O eluted with toluene/petrol 1:1 to give(2-chloro-4-methoxy-phenyl)-4-fluorophenyl-ketone (40%) as colourlesscrystalline solid m.p. 31°.

Stage 2. A solution of dimethyl sulphonium methylide was prepared undernitrogen at 0° C. from sodium hydride (0.03 mol using 80% suspension inoil), trimethyl sulphonium iodide (0.03 mol) in dry dimethyl sulphoxide(30 ml) and dry tetrahydrofuran (30 ml). A solution of(2-chloro-4-methoxyphenyl)-4-fluorophenyl ketone (0.02 mol) intetrahydrofuran (20 ml) was added at 0°, stirred for 30 minutes at 0°,and allowed to warm-up to room temperature. The solution was poured intowater, extracted with diethyl ether (150 ml), washed with water (3×100ml) and dried over anhydrous magnesium sulphate. Removal of the solventgave 1-(2-chloro-4-methoxy-phenyl)-1-(4-fluorophenyl)-ethylene oxide(90%) as a colourless oil. Stage 3. 1,2,4-Triazole (0.03 mol) was addedportionwise to sodium hydride (0.03 mol) in dimethyl formamide (30 ml)and the solution was stirred at room temperature until the effervescenceceased. 1-(2-chloro-4-methoxyl-phenyl)-1-(4-fluorophenyl)-ethylene oxide(0.015 mol) in dimethyl formamide (10 ml) was added dropwise and thesolution stirred at 80° for 4 hours. The solution was poured into waterand triturated with petroleum ether to an off-white solid which wasfiltered off and dried. Recrystallisation from petroleumether/chloroform gave the title compound (65%) as a white crystallinesolid m.p. 138°-140°.

EXAMPLE 8

This Example illustrates the preparation of:1-(1,2,4-Triazol-1-yl)-2-(4-chlorophenyl)-3,3-dimethyl-butan-2-ol(Compound No 196 of Table I).

Stage 1. Trimethyl acetonitrile (0.1 mol) in dry tetrahydrofuran (50 ml)was added dropwise with stirring to the Grignard reagent prepared form4-chloro-iodobenzene (0.11 mol) and magnesium turnings (0.11 g atoms) insodium dry ether (50 ml) at such a rate as to retain gentle reflux. Thesolution was refluxed for 4 hours, cooled to room temperature, and water(40 ml) added carefully. 2N H₂ SO₄ (50 ml) was added and the ethersolution washed with water (3×100 ml) and dried over anhydrous magnesiumsulphate. Removal of the solvent gave a yellow oil which was distilledat the water pump to give tertiary butyl 4-chlorophenyl ketone (40%) asa colourless liquid b.p. 116°-128°/15 mm Hg.

Stage 2. A solution of dimethyl oxosulphonium methylide was preparedunder nitrogen from sodium hydride (0.03 mol) and powdered trimethyloxosulphonium iodide (0.03 mol) in dry dimethyl sulphoxide (40 ml). Asolution of 4-chlorophenyl tertiary butyl ketone (0.025 mol) in drydimethyl sulphoxide (10 ml) was added dropwise at room temperature andthe solution heated at 50° C. for 2.5 hours. After cooling to roomtemperature the solution was extracted with ether (150 ml), washed withwater and dried over anhydrous sodium sulphate. Removal of the solventgave 1-(4-chlorophenyl)-1-t-butyl-ethylene oxide (95%) as a colourlessliquid.

Stage 3. 1,2,4-Triazole (0.04 mol) was added portionwise to sodiumhydride (0.04 mol) in dimethyl formamide (40 ml) and the solutionstirred at room temperature until the effervescence ceased.1-(4-chlorophenyl)-1-t-butyl-ethylene oxide (0.02 mol) in dimethylformamide (10 ml) was added dropwise and the solution stirred at 60° for3 hours. The solution was poured into water and triturated withpetroleum ether to give a white solid which recrystallised from 60/80petroleum ether gave the title compound (65%) m.p. 70°-3°.

EXAMPLE 9

This Example illustrates the preparation of:1-(1,2,4-Triazol-1-yl)-bis-2-(4-fluorophenyl)-2-methoxy-ethane.

Stage 1. A solution of dimethyl oxosulphonium methylide was preparedunder nitrogen from sodium hydride (0.1 mol) and powdered trimethyloxosulphonium iodide (0.1 mol) in dry dimethyl sulphoxide (100 ml). Asolution of 4,4'-difluorobenzophenone (0.08 mol) in dimethyl sulphoxide(40 ml) was added dropwise at room temperature and the solution heatedat 50° for 2 hours. After cooling to room temperature the solution wasextracted with diethyl ether (400 ml), washed with water (3×250 ml), anddried over anhydrous sodium sulphate. Removal of the solvent gave1,1-bis-(4-fluorophenyl)-ethylene oxide (95%) as a colourless oil.

Stage 2. 1,2,4-Triazole (0.1 mol) was added portionwise to sodiumhydride (0.1 mol) in dimethyl formamide (100 ml) and the solutionstirred at room temperature until the effervescence ceased.1,1-bis-(4-fluorophenyl)-ethylene oxide (0.05 mol) in dimethyl formamide(25 ml) was added dropwise and the solution stirred at 80° for 4 hours.The solution was poured into water and triturated with petroleum etherto give a white crystalline solid which was filtered off and dried.Recrystallisation from petroleum ether (60°-80°)/chloroform gave1-(1,2,4-triazole-1-yl)-bis-2-(4-fluorophenyl)-ethan-2-ol (70%) as awhite crystalline solid m.p. 170°-1°.

Stage 3. Sodium hydride (0.02 mol) was suspended in dry tetrahydrofuran(50 ml) and 1-(1,2,4-triazol-1-yl)-bis-2-(4-fluorophenyl)-ethan-2-ol(0.02 mol) added portionwise at room temperature. The solution waswarmed to 50° to complete the reaction. After cooling to roomtemperature methyl iodide (0.04 mol) was added dropwise at 20° and thereaction stirred at room temperature for 24 hours. The reaction waspoured into water (100 ml), extracted with diethyl ether (150 ml),washed with water (2×100 ml), and dried over anhydrous sodium sulphate.Removal of the solvent gave an oil which solidified on standing.Recrystallisation from petroleum-ether/chloroform gave the titlecompound (90%) as a white crystalline solid. m.p. 100°.

EXAMPLE 10

An emulsifiable concentrate was made up by mixing the ingredients, andstirring the mixture until all the constituents were dissolved.

    ______________________________________                                        Compound of Example 1    10%                                                  Ethylene dichloride      40%                                                  Calcium dodecylbenzenesulphate                                                                         5%                                                   "Lubrol" L               10%                                                  "Aromasol" H             35%                                                  ______________________________________                                    

EXAMPLE 11

A composition in the form of grains readily dispersible in a liquid,e.g. water, was prepared by grinding together the first threeingredients in the presence of added water and then mixing in the sodiumacetate. The resultant mixture was dried and passed through a BritishStandard mesh sieve, size 44-100, to obtain the desired size of grains.

    ______________________________________                                        Compound of Example 2   50%                                                   "Dispersol" T           25%                                                   "Lubrol" APN5           1.5%                                                  Sodium acetate          23.5%                                                 ______________________________________                                    

EXAMPLE 12

The ingredients were all ground together to produce a powder formulationreadily dispersible in liquids.

    ______________________________________                                        Compound of Example 3   45%                                                   "Dispersol" T           5%                                                    "Lissapol" NX           0.5%                                                  "Cellofas" B600         2%                                                    Sodium acetate          47.5%                                                 ______________________________________                                    

EXAMPLE 13

The active ingredient was dissolved in a solvent and the resultantliquid was sprayed on to the granules of China clay. The solvent wasthen allowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound of Example 4    5%                                                   China clay granules      95%                                                  ______________________________________                                    

EXAMPLE 14

A composition suitable for use as a seed dressing was prepared by mixingthe three ingredients.

    ______________________________________                                        Compound of Example 1    50%                                                  Mineral oil              2%                                                   China clay               48%                                                  ______________________________________                                    

EXAMPLE 15

A dusting powder was prepared by mixing the active ingredient with talc.

    ______________________________________                                        Compound of Example 2    5%                                                   Talc                     95%                                                  ______________________________________                                    

EXAMPLE 16

A Col formulation was prepared by ball-milling the constituents set outbelow and then forming an aqueous suspension of the ground mixture withwater.

    ______________________________________                                        Compound of Example 3    40%                                                  "Dispersol" T            10%                                                  "Lubrol" APN5            1%                                                   Water                                                                         ______________________________________                                    

EXAMPLE 17

A dispersible powder formulation was made by mixing together theingredients set out below and then grinding the mixture until all werethoroughly mixed.

    ______________________________________                                        Compound of Example 4    25%                                                  "Aerosol" OT/B           2%                                                   "Dispersol" A.C.         5%                                                   China clay               28%                                                  Silica                   40%                                                  ______________________________________                                    

EXAMPLE 18

This Example illustrates the preparation of a dispersible powderformulation. The ingredients were mixed and the mixture then ground in acomminution mill.

    ______________________________________                                        Compound of Example 1    25%                                                  "Perminal" BX            1%                                                   "Dispersol" T            5%                                                   Polyvinylpyrrolidone     10%                                                  Silica                   25%                                                  China clay               34%                                                  ______________________________________                                    

EXAMPLE 19

The ingredients set out below were formulated into a dispersible powderby mixing then grinding the ingredients.

    ______________________________________                                        Compound of Example 2    25%                                                  "Aerosol" OT/B           2%                                                   "Dispersol" A            5%                                                   China clay               68%                                                  ______________________________________                                    

In Examples 10 to 19 the proportions of the ingredients given are byweight.

There now follows an explanation of the compositions or substancesrepresented by the various Trade Marks and Trade Names mentioned above.

    ______________________________________                                        LUBROL L:      a condensate of nonyl phenol                                                  1 mole) with ethylene oxide                                                   (13 moles)                                                     ARMASOL H:     a solvent mixture of alkylbenzenes                             DISPERSOL T & AC:                                                                            a mixture of sodium sulphate and a                                            condensate of formaldehyde with                                               sodium naphthalene sulphonate                                  LUBROL APN5:   a condensate of nonyl phenol                                                  (1 mole) with naphthalene oxide                                               (5.5 moles)                                                    CELLOFAS B600: a sodium carboxymethyl cellulose                                              thickener                                                      LISSAPOL NX:   a condensate of nonyl phenol                                                  (1 mole) with ethylene oxide                                                  (8 moles)                                                      AEROSOL OT/B:  dioctyl sodium sulphosuccinate                                 PERMINAL BX:   a sodium alkyl naphthalene                                                    sulphonate                                                     ______________________________________                                    

EXAMPLE 20

The compounds were tested against a variety of foliar fungal diseases ofplants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cmdiameter minipots. A layer of fine sand was placed at the bottom of thepots containing the dicotyledonous plants to facilitate uptake of testcompound by the roots. The test compounds were formulated either by beadmilling with aqueous Disperson T or as a solution in acetone oracetone/ethanol which was diluted to the required concentrationimmediately before use. For the foliage diseases, suspension (100 ppmactive ingredient) were sprayed on to the soil. Exceptions to this werethe tests on Botrytis cinerea, Plasmopara viticola and Venturiainaequalis. The sprays were applied to maximum retention and the rootdrenches to a final concentration equivalent to approximately 40 ppma.i./dry soil. Tween 20, to give a final concentration of 0.05%, wasadded when the sprays were applied to cereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the diseases. An exception was the test on Erysiphegraminis in which the plants were inoculated 24 hours before treatment.After inoculation, the plants were put into an appropriate environmentto allow infection to take place and then incubated until the diseasewas ready for assessment. The period between inoculation and assessmentvaried from four to fourteen days according to the disease andenvironment.

The disease control was recorded by the following grading:

4=no disease

3=trace--5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease on untreated plants

The results are shown in Table II. A dash in the table thus "-"signifies that no test against the disease was conducted.

                                      TABLE II                                    __________________________________________________________________________    COM-                PIRI- PLASMO-                                                                              PHYTO-        CERCOSPORA                                                                             VENTURIA              POUND                                                                              PUCCINIA                                                                              ERYSIPHE                                                                             CULARIA                                                                             PARA   PHTHORA                                                                              BOTRYTIS                                                                             ARACHI-  INAE-                 NUM- RECONDITA                                                                             GRAMINIS                                                                             ORYZAE                                                                              VITICOLA                                                                             INFESTANS                                                                            CINEREA                                                                              DICOLA   QUALIS                BER  (WHEAT) (BARLEY)                                                                             (RICE)                                                                              (VINE) (TOMATO)                                                                             (TOMATO)                                                                             (PEANUT) (APPLE)               __________________________________________________________________________     1   4       4      1     0      0      3      4        3                      2   4       4      0     0      0      3      3        --                     3   4       4      1     0      0      3      4        3                      4   3       4      0     4      0      3      4        3                      5   4       4      1     4      0      3      3        4                      5   4       4      3     2      0      3      4        --                     8   4       --     3     4      3      3      4        3                      9   3       4      2     0      0      2      3        3                     10   4       4      3     0      --     3      4        4                     11   4       4      3     0      1      4      4        4                     12   4       4      --    0      0      4      4        4                     13   4       4      3     3      0      3      4        3                     14   4       4      1     0      1      4      4        3                     15   4       4      1     0      2      3      4        3                     16   4       4      4     0      0      3      4        0                     17   --      4      --    0      0      1      4        4                     18   4       --     3     0      0      3      4        3                     19   4       4      3     3      0      --     4        4                     20   4       4      4     0      0      3      4        3                     21   4       4      3     1      0      4      4        4                     22   4       4      4     0      2      3      4        4                     23   4       4      3     0      0      3      4        4                     24   --      4      3     2      0      0      0        2                     25   4       4      2     0      0      3      4        4                     26   3       4      2     4      0      3      4        4                     27   4       4      3     1      0      4      4        4                     28   4       4      2     0      0      4      --       --                    29   --      4      3     0      0      3      4        4                     30   --      4      3     0      0      3      4        4                     31   4       4      2     0      0      0      3        4                     32   3       4      0     --     0      2      4        4                     34   4       3      4     2      0             4        4                     35   4       4            0      0      3      4        4                     40   3       4      2     0      1      0      4        4                     43   4       4            0      0      2      4        4                     44   4       3      4     1      0             4        4                     45   4       4      --    0      0      2      4        4                     46   4       4      --    1      0      3      4        4                     51   4       4      --    4      1      4      4        4                     52   4       4      --    0      3      2      4        4                     53   4       4      --    4      2      3      4        4                     54   4       4      --    3      2      2      4        4                     55   4       4      --    4      2      4      4        4                     57   3       4      --    0      0      0      0        0                     58   4       4      --    0      0      0      3        3                     59   3       4      --    1      0      0      3        3                     60   4       4      --    0      0      2      4        4                     __________________________________________________________________________    COM-                PIRI- PLASMO-                                                                              PHTYO-        CERCOSPORA                                                                             VENTURIA              POUND                                                                              PUCCINIA                                                                              ERYSIPHE                                                                             CULARIA                                                                             PARA   PHTHORA                                                                              BOTRYTIS                                                                             ARACHI-  INAE-                 NUM- RECONDITA                                                                             GRAMINIS                                                                             ORYZAE                                                                              VITICOLA                                                                             INFESTANS                                                                            CINEREA                                                                              DICOLA   QUALIS                BER  (WHEAT) (BARLEY)                                                                             (RICE)                                                                              (VINE) (TOMATO)                                                                             (GRAPE)                                                                              (PEANUT) (APPLE)               __________________________________________________________________________    62   4       4      --    0      0      3      4        4                     64   3       4      --    0      0      0      0        3                     65   4       4      --    0      0      4      3        4                     66   4       4      --    0      1      0      4        4                     67   4       4      --    0      0      2      4        4                     69   4       4      --    0      0      4      4        4                     70   4       4      --    0      0      4      4        4                     71   3       4            0      0      3      4        4                     72   4       4      --    0      0      0      3        4                     75   4       4      --    3      0      2      4        4                     81   4       3      --    0      0      4      4        4                     82   4       4      --    0      0      4      4        4                     83   4       4      --    0      0      4      4        4                     85   4       4      --    1      0      3      4        4                     86   4       4      --    3      --     4      4        4                     87   4       4      --    3      --     4      4        4                     89   4       4      --    3      0      3      4        4                     90   4       4      --    0      0      3      4        3                     91   4       4      --    0      0      4      4        4                     97   3       4      --    0      --     2      4        4                     102  4       4      --    1      --     4      3        4                     103  4       4      --    0      0      4      4        4                     104  4       4      --    0      0      0      3        4                     105  4       4      --    0      0      0      4        4                     107  4       4      --    1      0      0      4        4                     108  4       4      --    0      0      4      4        4                     109  4       4      --    3      0      1      4        4                     110  4       4            0      0      4      4        4                     111  4       4      --    2      --     0      2        4                     112  4       4      --    3      --     0      0        4                     117  4       4      --    0      --     0      1        4                     118  4       4      --    4      --     0      4        4                     121  4       4      --    1      1      0      4        4                     122  0       4      --    0      0      0      2        2                     123  0       4      --    3      1      0      1        2                     125  4       4      --    3      --     0      3        4                     128  4       3      --    1      0      --     4        4                     129  4       4      --    0      0      4      4        4                     130  4       4      --    1      0      3      4        4                     131  4       4      --    0      0      0      2        2                     132  4       4      --    0      --     0      3        4                     133  4       4      --    0      --     --     3        4                     139  4       4      --    0      0      0      4        4                     140  4       4      --    0      0      4      3        4                     142  4       3      --    0      0      1      4        3                     147  4       4      --    3      0      0      4        4                     167  4       4      --    0      0      1      4        4                     168  4       4      --    --     --     0      3        4                     176  4       4      --    0      0      0      4        4                     177  4       4      --    4      0      1      4        4                     178  4       4      --    0             4      4        4                     179  4       4      --    2      0      4      4        4                     195  4       4      --    2      0      4      4        4                     196  4       4      --    0      0      4      4        4                     198  4       4      --    3      --     0      4        4                     204  4       4      --    0      --     0      4        4                     228  4       4      --    1             2      3        4                     235          4      --           0      4      4        4                     236  4       4      --    0      0      4      4        4                     244  4       4      --    1      0      3      4        4                     248  4       4      --    3      3      4      3        4                     250  2       4      --    0      0      0      1        0                     251  4       4      --    0      0      2      4        4                     252  4       4      --    0      0      4      4        4                     253          4      --    0      0      4      4        4                     254  4       4      --    0      0      2      4        4                     255  4       3      --    0      0      1      3        3                     256  4       4      --    0      0      2      4        4                     257  4       4      --    0      0      3      4        4                     258  4       4      --    2             4      4        4                     259  4       4      --    0      --     3      4        4                     260  3       4      --    3      --     2      4        4                     261  3       4      --    1      --     4      4        4                     262  4       4      --    0      --     4      4        3                     263  4       4      --    0      0      2      4        4                     264  4       4      --    2      --     1      4        3                     265  3       4      --    0             1      1        0                     266  4       4      --    0      --     0      --       4                     267  4       4      --    0      --     4      --       4                     268  4       4      --    0      --     4      --       4                     269  4       4      --    0      0      4      4        4                     270  4       4      --    4      3      4      4        4                     271  4       4      --    4      0      4      4        4                     272  3       4      --    0      0      0      4        3                     273  4       4      --    0      0      3      3        4                     274  3       4      --    2      0      2      0        4                     275  4       4      --    0      --     0      4        4                     276  4       4      --    3      0      4      4        4                     277  4       4      --    3      --     --     4        4                     279  4       4      --    2      --     0      3        4                     280  4       4      --    2      0      3      3        3                     281  3       4      --    3      --     0      4        4                     282  4       4      --    3      --     --     3        4                     284  4       4      --    0      0      1      4        4                     285  4       4      --    1      0      4      3        4                     286  1       4      --    0      1      0      0        0                     287  3       4      --    0      0      0      0        0                     288  4       4      --    0      --     0      4        4                     289  4       4      --    0      --     0      3        4                     290  4       4      --    0      --     0      1        4                     291  4       4      --    1      --     0      1        4                     292  4       4      --    3      --     0      4        4                     293  4       4      --    0      --     --     4        4                     294  4       4      --    0      --     0      4        4                     295  4       4      --    0      --     0      3        3                     296  4       4      --    0      --     0      4        4                     297  4       4      --    2      --     0      4        4                     301  4       4      --    0      --     0      4        4                     302  4       4      --    0      --     --     2        3                     303  0       3      --    1      --     --     0        0                     __________________________________________________________________________

EXAMPLE 21

This Example illustrates the plant growth regulating properties of thecompounds. The compounds were applied in the form of a 4000 ppm solutionin distilled water and the solution was then applied to the foliage ofyoung seedlings of various plants. The experiments were replicatedtwice. After 12 or 13 days from treatment the plants were assessed forplant growth regulating effects and phytotoxic symptoms.

Table III shows the stunting effect of the compounds on the vegetativegrowth using the following grading:

1=0-30% retardation

2=31-75% retardation

3=75% retardation

If no figure is given, the compound was substantially inactive as astunting agent. Additional plant growth regulating properties areindicated as follows:

G=darker green lead colour

A=apical effect

T=tillering effect.

                                      TABLE III                                   __________________________________________________________________________    COM-                                                                          POUND                                                                         NUM-           SUGAR                                                                              AGROSTIS                                                                             CYNODON                                                                              DACTYLIS                TO-                                                                           -BER SOYA COTTON                                                              7BEET TENUIS DAC                                                              TYLON GLOMERATA                                                               WHEAT BARLEY MAI                                                              ZE MATO             __________________________________________________________________________     1             3G   2G                    1               G                    2   1         2G   1      1                         2    1G                   6   1         3G   3      2G     2G      1G              3G                   9   2G  G     1    1G     1G     1G           1T         2G                  11   2G  1G    3G   3G     3G     3G                      3G                  12   1         3G   2G     1G     1       2    T          3G                  13   1G  2     1G                         1GT        2    2                   14   1G        2G   1G     1G     1G      1          2    3G                  15   2G        3G   1      2      1                  1    2GA                 17   G   2     2G                                         G                   18             3    2G     2G     1       1    1     2    3G                  19   2G  2     2GT  2      1              1               3GA                 20   2G  2G    2G   2      2      2            1     1    3GA                 21   2G  2G    2G   2G     2G     2G      1    1     1    3A                  23   1   2     1G   1      1      1                       2GA                 25   2G  3G    3GA  1      1              T          3    2G                  26   G   2G    1G                                    3    3                   27   1G        2G                                    1    3G                  28             2G                                    1    2G                  31   3GA 2G    1G                         T    1     3    3G                  32   2G  2     3G   3G     1              1    1     1    3GA                 34   2GA 1G    2G   2G     2G     2G                 3    3GA                 35   2G  2G    3GA  3G     3G     2G      1    1     2    3G                  41   1G  1G    1G   1                                1    2                   42             1G                                         1G                  44   1GA G     3G          1G             T          1    3GA                 46   2GA G     2G                         1T              2GAT                49       2G    1G   1                     1GT  1GT        2G                  50   1   2G    2G                                         1G                  52             1                               T     1                        53       1G    3G                              T     1    2G                  54   G   1G    2G                              T     2    3G                  55   1G  3G    3G                         1          1    3A                  69             G                                                              70             1G                                                             71   1G  1G    1G                              1     1    2G                  75             1G   G                                     1GT                 81             YG                              1          2G                  85       2GA   3GA                                   2G   3GT                 89       2G    2G   1      1                   1G         1G                  90   1G  2G    1G   1      2      1       1    1G         1G                  104  1T                                              1                        105      1G    1G                                    1                        107            2G                                    1    1G                  108            3GA                                   1    2G                  109            3G                                         3G                  128  2G  2G    2G   2G     2G     1G                      3GA                 129  3G  2G    2GAT 3G     3G     2G      1T         1    3G                  147  2   1                                1               2                   177  2G  1                                           1    2                   196  2G  3G    3G   1                     1G   1G    1    3GA                 248  2G  2G    3G   3G     2G     2G      3G   1G         3GA                 250      G                                                                    251  1G  2G    2G                              1          2GA                 252  1GT 1GA   3GA                                   2    2GT                 __________________________________________________________________________

We claim:
 1. A compound of formula (1) ##STR13## wherein R¹ is C₁ -C₆alkyl, halophenyl, cyclobutyl, cyclopropyl or cyclopentyl and R² ishalophenyl or halophenyl substituted by C₁ -C₆ alkyl or C₁ -C₅ alkoxy,in the form of an ether which is a C₁₋₆ alkyl ether, a C₃₋₄ alkenylether or a benzyl ether wherein the benzyl is unsubstituted orsubstituted with chlorine, or in the form of an ester which is analkanoyl, alkenoyl or alkynoyl, each of 1 to 4 carbons, or benzoyl orhalo- or nitro-substituted benzoyl ester thereof.
 2. A compound offormula (1): ##STR14## wherein R¹ is C₁ -C₆ alkyl, R² is halophenyl andR¹¹ is C₁ -C₆ alkyl.
 3. An ether or ester according to claim 1 whereinR¹ and R² are both halophenyl.
 4. An ether or ester according to claim 1wherein R¹ and R², which may be the same or different, are eachchlorophenyl or fluorophenyl.
 5. An ether or ester according to claim 1of the compound1-(1,2,4-triazol-1-yl)-2-(4-fluorophenyl)-2-(4-chlorophenyl)ethan-2-ol.6. An ether or ester according to claim 1 of the compound1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)ethan-2-ol.7. An ether or ester according to claim 1 of the compound1-(1,2,4-Triazol-1-yl)-2-(4-fluorophenyl)-2-(2,4-dichlorophenyl)ethan-2-ol8. An ether or ester selected from the ethers and esters of thecompounds1-(1,2,4-Triazol-1-yl)-2,2-di(4-fluorophenyl)ethan-2-ol,1-(1,2,4-Triazol-1-yl)-2-(4-chlorophenyl)-2-(2-chlorophenyl)ethan-2-ol.1-(1,2,4-Triazol-1-yl)-2-(4-fluorophenyl)-2-(2-chlorophenyl)ethan-1-ol.1-(1,2,4-Triazol-1-yl)-2-(2-chloro-4-methoxyphenyl)-2-(4-fluorophenyl)ethan-2-ol.1-(1,2,4-Triazol-1-yl)-2-(4-fluorophenyl)-2-(2-fluoro-4-methyl-phenyl)ethan-2-ol,or1-(1,2,4-Triazol-1-yl)-2-(4-fluorophenyl)-2-(2-chloro-4-methyl-phenyl)ethan-2-ol.9. C₁₋₄ alkyl ethers and acetyl esters of compounds according toclaim
 1. 10. A fungicidal composition characterized in that itcomprises, as an active ingredient, an effective amount of ether orester as defined in claim 1, together with a carrier or diluent.
 11. Amethod of combating fungi, especially fungal diseases in a plant, whichmethod comprises applying to the plant, to seed of the plant or to thelocus of the plant or seed an effective amount of ether or esteraccording to claim
 1. 12. A plant growth regulating compositioncharacterized in that it comprises, as an active ingredient, aneffective amount of ether or ester as defined in claim 1, together witha carrier therefore.